Monoazo-dyestuffs



2,320,735 C Patented Jan. 21, 19 58 United States Patent 2 2,820,785 Thus, diazo-compounds which contain a cyanuric acid AZ E TU S radical and are especially valuable for the present process, Heinrich Zoning", Bi i and Alf d F i fi B are obtainable, for example from diamines of the benzene mingen, Switzerland, assignors to Ciba Limited, Basel, series by reacting the diamine with 1 molecular propor- Switzerland, :1 Swiss firm 5 tion of cyanuric chloride, and in the resulting primary No Drawing. application August 9, 1954 condensation product exchanging a remaining chlorine $8.113]. No. {48,738 atom for the radical of an aliphatic, alicyclic, araliphatic Chums Priority, application Switzerland August 1953 or aromatic compound advantageously containing at most ciaims- 12 carbon atoms and containing a reactive hydrogen atom. Thi invention rovides monoazo-dyesmfis whi h, like 10 As compounds containing at most 12 carbon atoms there the product of the formula come into consideration, for example, ammonia, aliphatic (l) v /N\ H0 N=N O-NH 3 0-01 NH: I N\ sm-O-cn; Hot Nil-O correspond to the general formula or aromatic hydroxy compounds, mercaptans, and above (2) all organic nitrogen compounds such as amines, amides,

in which R represents the radical of an aminonapbthalene ammiyalcuhols ammo'aclds urethanes and the like It sulfonic acid bound to the azo linkage in a position vicinal to the amino group, R represents the radical of a diazo component of the benzene series, X represents a heterocyclic radical having no dyestufl character and bound to R through a nitrogen bridge, and which radical contains a reactive halogen atom and a single hetero cyclic ring.

The invention also includes a process for making the aforesaid monoazo-dyestufis, wherein an aminonaphthalene sulfonic acid (such as 2-aminonaphthalene-3z6- or 3 :7-disulfonic acid, 2-amino-8-hydroxynaphthalene-3 :6- disulfonic acid, and especially aminonaphthalene monosulfonic acids such as 2-amino-3- or -5-hydroxynaphthalene- 7-sulfonic acid, 2-amino-7-hydroxynaphthalene-4-sulfonic acid, 2-aminonaphthalene-6-, -7- or -8-sulfonic acid, 2- alkylaminoor 2-arylamino-S-hydroxynaphthalene-6-sulionic acids, for example, 2-methylamino-, Z-B-hydroxyethylaminoor Z-phenylamino-8-hydroxynaphthalene-6- sulfonic acid, and especially 2-amiuo-8-hydroxynaphthalene-6-sulfonic acid itself) is coupled in an acid medium Wlth a dlazo compound of the formula and of which the diazo-compounds are used as starting 2 1 materials in the present process, there may be mentioned: in Which 1 and X have the meanings given above in 45 The condensation product from 1 mol of 2:4-dichlorowith these compounds first, whereby a cyanuric halide of the Formula 4 is formed, which is simultaneously or sub sequently condensed with 1 molecular proportion of the diamine.

It is often of advantage to use as starting materials monaminoor monhydroxy-benzenes which contain a substituent convertible into an amino group (for example a nitro or acylamino group), and, after the condensation with the cyanuric halide, to convert the latter substituent into an amino group, for example, by reduction or bydrolysis. As such monaminoor monhydroxy-benzenes there come into consideration, for example, 3- or 4- formylamino-l-aminobenzene.

The condensation with the cyanuric halide is advantageously carried out in the presence of an acid-binding agent such as sodium carbonate. In this condensation it will be understood that it must be carried out so that at least one exchangeable halogen atom remains in the finished product.

As examples of amines obtainable as described above,

nection with Formula 2. quinazoline and 1 mol of 1:4 diaminobenzeneQ-sulfonic The amin s 0f t FOfmllia which are used as Start acid, a condensation product from 1 mol of 2:4-dichloroing materials in the Present Process, can be P p y quinazoline and 1 mol of 2:S-diaminobenzene-l-sulfonic methods in t emse es known, for example, by condensacid-N-ethyl-anilide or 1 mol of 2:5-diamino-l:1-diing 1 molecular proportion of an amine which contains h l lf e in addit on to the diaZOiiZabie amino p, a reactive Especially valuable monoazo-dyestufis are obtained y g atom bound to nitrogen atom, with 1 molecu' with secondary condensation products from 1 mol of any' lar proportion of a heterocyclic halogen-compound havone f h f ll i i i g 110 dyesiuii character, which contains a Single hetero l:4-diaminobenzene-Z-sulfonic acid, 1:3-diaminobencyclic ring and at least two reactive halogen atoms, for example with 1 molecular Proportion of wrdichlowdiaminodiphenylmethane, 4:4 dimethyl-3:3-diaminodi quinoline, lz4-dichlorophthalazine, methyldichloropyrimih l th 4:4-diamin0diphenyl, 4:4'- or 2:4'-di dine, 2:4-dichloroquinazoline, 2:4:7-trichloroquinazoline, aminodiphenyl ether, 4:4'-dichloro-2:2'-diaminodiphenyl triChl0r0- 0 il'ibromo'pyrimidihe, zii'dichiol'opyrimidine e0 ether, 4:4'- or 2:2-diamin0dipbenylsulfide, 4:4'- or 3:3- and above all 2i4i6-trichloio-ll3i5-iiiazine with 1 diaminodiphenyl sulfone, 2:S-diaminobenzene-l-methyl is of advantage, however, to carry out the condensation zene-4-sulfonic acid, 1:3- or 1:4-diaminobenzene, 4:4'-l

molecular proportion of a cyanuric halide of the formula sulfone, 2:5-diaminobenzene-l-ethyl sulfone, 2:5-diamino- (4) N 4-methoxy-1:l'-diphenyl sulfone, 2:5-diarnino-4'-methylli-fi/ o-nalo on 1:l'-diphenyl sulfone, 2:5-diamino-1: l'-diphenylsulfone,

N 2:S-diaminobenzene-l-sulfonic acid amide, 2:5-diamino benzene-l-sulfonic acid methyl-, -ethyl, -phenylor -para- 0 tolylamide, 2:S-diaminobenzene-l-sulfonic acid dimethylhalogen or -diethylamide, 2:5diaminobenzene-l-sulfonic acid ey in which A represents an aliphatic, alicyclic, araliphatic ciohexyiamide, i f q e 1 sulfonic acid-N or aromatic radical advantageously containing at most 12 y ethyiamhde, with 1 moi of a p y COIP' carbon atoms and bound to the triazine nucleus through densation product from cyanuric chloride and 1 mol i.

an oxygen, sulfur or nitrogen bridge. one of the following compounds: Alcohols and phenols br sul fones of these acids. v Theamines used las tstarn'ng materials in the present process can be diazotized by methods in themselves known, for example, with the aid of mineral acids, especially hydrochloric acid and sodium nitrite, or by one of the usual methods applicable to compounds which are difi'lcult to diazotize, for example, with the aid of nitrosylsulfuric acid. In the latter case it is often of advantage the precipitated diazo-compound, and then-coupling with the il-'am'inoiiaphthalene sulfonic acid. The coupling is carried out in an acid medium, for example, an acetic acid medium or a medium rendered weakly acid to Congo. For this purpose, for example, a 2-amin0naphthal'ene sulfonic acid may first be converted into an alkali salt, reconverted into the free acid by the additi'onof acetic acid, whereby a suspension is obtained, and then coupling the filtered-E diazo compound with this suspension. The free mineral acid "liberated during the coupling reaction is then neutralized, for example, with sodium acetate and if desired, the temperature is raised somewhat. I

The isolation --'of :the dyestutr' from thecoupling mixture is carried out in such manner that the isolated product stillcontains a 'reactive halogen atom. For this purpose there is added to the coupling mixture, for example,

be :made by a r'nodification of the above process, wherein 1 molecular proportion of a monoazo-dyestufi of the formula in WhlChTRfICPI'CSCDtS the radical'ofan a'minonap'hthalene sulfonic acid bound to the azo linkage in a position vicinal :to the amino group-R represents the radical of a diazo component of the benzene'series, and Z represents an amino group containing at-least one reactive hydrogen atom, is condensed with 1 molecular proportion of a heterocyclic halogen-compound which contains a single heterocyclic ring and at least two exchangeable halogen atoms, and, ifthe resulting product contains two exchangeable halogen atoms, exchanging one of these halogen atoms by condensation with an aliphatic, cycloaliphatic, araliphatic or "aromatic compound which contains a reactive hydrogen atom. i

The monoazo dyestuffs-of the Formula used as starting materials can be made. -by methods in themselves known by coupling one of the aminoaphthalene sulfonic acids mentioned above in'an acid medium with a diazo compound, which contains,inaddition to the diazo group, afree amino group, or a substituent convertible into a free amino group,-suchsubstituent being so converted after the coupling reaction.

As examples of such --diazo-compounds there may be mentioned those obtainable from the 'following amines: 3- M or 4-nitro-1eaminobenzene, 4-nitro-4'-aminodiphenyl and the diamines mentioned above or their mono'acyl compounds.

The condensation of the monoazo dyestufis of the Formula 5 so obtained with the vheterocyclic halogen- 4 I I I compounds which contain .a single heterocyclic ring and at least two halogen atoms, and of which the more easily accessible examples are mentioned above, is advantageously carried out in the presence of an acid-binding agent such as sodium acetate and under conditions such that the resulting dyestufi? condensation'product contains a reactive halogen atom, thatisto say, for example, in

an organic medium or in an aqueous medium at as low 7 a temperature-as possible.- I I p I I The new dyestuffs of this invention are suitable for dyeing and printing a very wide variety of materials, especially those of animal origin, such as leather, silk and above all wool, and also various artificial fibers, for example, animalized artificial silk, superpolyarnides,;-or super-polyurethanes, etc. The dyeings and prints obtain? able with these dyestufis, especially those which contain only one sulfonic acid group and -a sing-lehalogen atom,

are distinguished by their valuable tints, their level charactor and their good fastnessto washing and fulling, especially in the alkaline region.

The following examples illustrate the invention, the parts and percentages being by weight unless otherwise stated, and the relationship of parts by weight to parts by volume being the, same as thatof the kilogram to the liter: I Example] 39.3 partsof secondary condensation product from 1 mol of cyanuric chloride, 1 'mol of aniline and 1 mol of l 23-diaminobenzene-4-sulfonic acid .are suspended in 300 parts of water and 20 parts of hydrochlor'ic'acid of 30 percent strength .and diazotized at about 10-15" with 25 parts by volume of a 4N-solution of sodium nitrite. The resulting slightly yellowish diazo-suspension is mixed with 30 parts ofsodium acetate v (CI-1 COO.I la.3H O) and then at 20-25" with a solution rendered acid with acetic acid of the sodium 'sa1to'f .23.9 :parts of Z-amino- 8ahydroxynapthalene-o sulfonic acid in 200 parts of water. When the coupling is finished the suspension is rendered weakly alkaline tolitmus with sodium carbonate solution, salted out and :fi-lteredoif. There is obtained a dyestuir' which dyes Wool from sulfuric acid or acetic acid baths red tints of excellent fas'tness to. light and good properties of wet fas'tness. I 7 By using instead of the condensation product from equivalent parts of cyanuric chloride, aniline and 1:3- diaminobenzene-4 sulfonic acid, the condensation product from cyanuric chloride, 'aniline and 1:4-diaminobenzene- 2-sulfonic acid, there isobtained adyestufi yielding somewhat more bluish shades :and having similar properties of fastness.

5E Q: HO I fliGs l lczm. ,l V I V 7 Isoin are dissolved in the form-o'f-tlre sodium salt in 2000 parts N i I are added at 3545 C. I 'he whole 'is stirred at the temperature 'for' 4-6 hours, 'and :the mineral a'cid'formed is neutralized with a solution of sodium carbonate on sodium acetate. 'When'the condensation :is finished, the dyestufi is salted out with sodium chloride, filtered and dried. It dyes wool fi'om weakly acid or neutral baths bluish red tints which are distinguishedbyitheif" Similar dyestuffs are obtained by using, instead of the condensation product from cyanuric chloride, aniline,

and 1:4-diaminobenzene-Z-sulfonic acid-N-ethyl'phenylamide, the condensation products mentioned in "denim I, and using the same coupling component. In column III are given the tints obtainable on wool. a

I n "In Dime-components Coupling components Tlntsof dy g-s N 1 01-0 C-NH- 2-amin0-8-hydroxy- Blulshted.

| naphthalene-64ml- N N fonlcacld.

I NRO so CH: 2 01-? lC-NH d0 D0.

E NH@ soz-b r-cna 3 cl-tll '3NH do Do.

F I HaCNCHa SOz-N--CgH5 4... 01-? ?NH do D0.

NH \c'} I 3 NHQ SOr-N-Cglih s C1C|} (J-NH do Do.

5 NH-C Ha S O2N- C 2 5 )K' 6 (II-(l3 53-NH- do Red.

NH- S0r-N-Cz 5 I II III Blaze-components Coupling components Tintsoi dyelngs 14--- ClC C-NH- do Yellow-15h l I red. N

C d-@ SOi-N-CIHI 15. Condensation product of cyanuric chloride, do Red.

N -methyl aniline and 2:5-dlaminobenzenel-sulionic acid N ethylanllide.

Examplej necessary for the diazo-component can be prepared in 44.5 parts of the condensation product from 1 mol of cyanuric chloride, 1 mol of monomethylamine and 1 mol of 2:S-diaminobenzene-l-sulfonic acid N ethylphenylamide are stirred in 300 parts of an aqueous sulfuric acid which contains 10 percent of H 80 and a quantity of a commercial naphthalene monoor -poly-sulfonic acid suiticient for partial dissolution of the diazo-component. An aqueous solution of 6.9 parts of sodium nitrite is added dropwise to the suspension slowly while stirring. The resulting diazo-compound is in part dissolved.

After any excess of nitrous acid has been decomposed with urea, there is added a neutral suspension of 22.3 parts of Z-aminonaphthalene-o-sulfonic acid and the necessary quantity of sodium carbonate in 50 parts of water, and the mineral acid is neutralized by the addition of sodium acetate until Congo paper no longer turns blue. In order to accelerate the coupling the reaction mixture may be warmed to a temperature of about 50 C. When the coupling is finished, the mixture is neutralized by the addition of sodium carbonate. The precipitated red brown dyestufi is filtered oil in the usual manner and dried. The dyestufi so obtained dyes wool from acetic acid baths reddish orange tints which are fast to light.

A dyestufi, which dyes wool somewhat less reddish orange tints, is obtained by using, instead of 2-aminonaphthalene-6-sulfonic acid, 22.3 parts of Z-aminonaphthalene-S-sulfonic acid.

By using for coupling with the same diazo-compound 25.3 parts of Z-methylamino-S-hydroxynaphthalene-6- sulfonic acid there is obtained a dyestufi which dyes wool violet tints which are fast to light.

Example 4 48.1 parts of the condensation product from 1 mol of cyanuric chloride, 1 mol of aniline and 1 mol of 2-amino- -methylamino-4'-methyl-diphenyl sulfone are stirred in 300 parts of aqueous sulfuric acid which contains 10 parts of H 50 and also a quantity of a commercial naphthalenemonoor -poly-sulfonic acid sufiicient only for partial dissolution of the diazo-component. An aqueous solution of 6.9 parts of sodium nitrite is added dropwise slowly to the mixture while stirring.

When the diazotization is finished, any excess of nitrous acid is decomposed, and a weakly acid suspension of 23.9 parts of Z-amino-8-hydroxynaphthalene-o-sulfonic acid in 50 parts of water, is added. By the addition of the necessary quantity of sodium acetate the mixture is maintained at a pH value between 2.0 and 4.0. When the coupling is finished, the mixture is neutralized by the addition of sodium carbonate, and the dyestuff is salted out in the usual manner and isolated. It is a dark red-brown powder which dyes wool from acetic acid baths bluish red tints which are fast to light.

The 2-amino-S-methylamino-4'-methyl-diphenylsulfone known manner by reacting 2:5-diamino-4'-methyl-diphenylsulfone with an equivalent quantity of a methyl halide, for example methyl iodide.

Example 5 In a manner analogous to that described in Example 4, the diazo-compound obtained from 37.5 parts of the condensation product from 1 mol of 2:5-diamino-4' methyl-diphenylsulfone and 1 mol of 2:4-dichloropyrimidine is coupled with 23.9 parts of 2-amino-8-hydroxynaphthalene-d-sulfonic acid in an acid medium.

The dyestufi so obtained dyes Wool from acetic acid baths distinctly more yellowish tints than those of the dyestuffs described in Examples 2 and 4 prepared with diazo-compounds derived from 2:5-diamino-4-methyl-di phenylsulfone.

Example 6 2. parts of the dyestufi obtained as described in Example 2 are dissolved in 4000 parts of water, 10 parts of crystalline sodium sulfate are added to the dyebath, and parts of wool are entered at 40 50 C., 2 parts of acetic acid of 40 percent strength are then added, the temperature is raised to the boil in the course of /2 hour and dyeing is carried on at that temperature for hour. By rinsing and drying the material there is obtained a blue-red dyeing which is fast to light, and possesses very good fastness to washing and fulling.

What is claimed is:

1. A monoazo dyestufi of the formula in which R represents the radical of an aminonaphthalene monosulfonic acid bound to the azo linkage in a position vicinal to the amino group, R represents the radical of a diazo component of the benzene series free from sulionic and carboxylic acid groups, and X represents a triazine radical bound through a nitrogen bridge to R and which contains an exchangeable chlorine atom and, as single heterocyclic ring, the ring of the said triazine radical.

2. A monoazo dyestufi which contains a single free sulfonic acid group and corresponds to the formula in which R represents the radical of a Z-aminonaphthalene monosulfonic acid bound to the azo linkage in l-position, Y represents a member of the group consisting of a sulfone and a sulfonic acid amide group, and A represents a member of the group consisting of a hydrogen atom,

wherein n is a whole number up to and including 2.

3. A'monoazo dyestuif which contains a single free sulfonic acid group and corresponds to the formula monosulfonic acid bound to the azo linkage in l-position, Y represents a sulfonic acid amide group and A represents a benzene radical bound to the triazine nucleus d through an -NH- group.

" 4. A monoazo dyestuif of the formula in which R and A each represent a benzene radical free from water-solubilizing groups and n represents a whole number up to 2.

6. A monoazo dyestufi of the formula "12 in which R represents a benzene radical free from watersolubilizing groups and X, Y and Z each represent an alkyl radical of at most two carbon atoms. 7. The monoazo dyestuff of the formula 803K I 15 8. The monoazo dyes-tuft of the formula NH, V

g a r -Q 0 N N s0;--N-GH= 0H 503K 9. The monoazo dyestuff of the formula A NHQ i /N\ /CHs N=NONHC c-N l H I N N CH: SOr-N-CzHa 10. The monoazo dyestuff of the formula on SOzH References Cited in the file of this patent UNITED STATES PATENTS Fritzsche et .al. Apr. 24, 1928 Gubler et a1. Aug. 1, 1937 

1.A MONOAZO DYESTUFF OF THE FORMULA 